2026-09-14T13:00:31Zhttps://gredos.usal.es/oai/request

oai:gredos.usal.es:10366/1467642026-01-20T16:48:06Zcom_10366_138663com_10366_4512com_10366_3823col_10366_138665

Ortega Álvarez, Pablo Gil-Guerrero, Sara Veselinova Marinova, Anzhela Zanchet, Alexandre González Sánchez, Lola García Jambrina, Pablo Sanz-Sanz, Cristina 2021-06-11T08:08:48Z 2021-06-11T08:08:48Z 2021 P. Ortega, S. Gil-Guerrero, A. Veselinova, A. Zanchet, L. González-Sánchez, P. G. Jambrina, C. Sanz-Sanz; Multi- and single-reference methods for the analysis of multi-state peroxidation of enolates. J. Chem. Phys. 14 April 2021; 154 (14): 144303. https://doi.org/10.1063/5.0046906 0021-9606 http://hdl.handle.net/10366/146764 10.1063/5.0046906 1089-7690 [EN]In spite of being spin-forbidden, some enzymes are capable of catalyzing the incorporation of O2(Σg−3Σg−3) to organic substrates without needing any cofactor. It has been established that the process followed by these enzymes starts with the deprotonation of the substrate forming an enolate. In a second stage, the peroxidation of the enolate formation occurs, a process in which the system changes its spin multiplicity from a triplet state to a singlet state. In this article, we study the addition of O2 to enolates using state-of-the-art multi-reference and single-reference methods. Our results confirm that intersystem crossing is promoted by stabilization of the singlet state along the reaction path. When multi-reference methods are used, large active spaces are required, and in this situation, semistochastic heat-bath configuration interaction emerges as a powerful method to study these multi-configurational systems and is in good agreement with PNO-LCCSD(T) when the system is well-represented by a single-configuration. eng info:eu-repo/semantics/openAccess Triplet state Full configuration interaction Density functional theory Configuration interaction Correlation-consistent basis sets Minimum energy path problem Potential energy surfaces Potential energy barrier Multi- and single-reference methods for the analysis of multi-state peroxidation of enolates info:eu-repo/semantics/article